CN102959144A

CN102959144A - High molecular weight polyethylene fibers and membranes, production and use thereof

Info

Publication number: CN102959144A
Application number: CN2011800316600A
Authority: CN
Inventors: D·罗伯特; J·哈芬; K·鲁德克; J·埃勒斯
Original assignee: Ticona GmbH
Current assignee: Ticona GmbH
Priority date: 2010-07-06
Filing date: 2011-07-01
Publication date: 2013-03-06
Also published as: BR112012032615A2; WO2012004674A3; JP2013531111A; EP2591154A2; US8993704B2; KR20130122905A; US20130079483A1; WO2012004674A2

Abstract

In a process for producing an elongated polyethylene component, such as a fiber or membrane, polyethylene powder having a molecular weight of at least 3 x 105 g/mol as determined by ASTM 4020 is dissolved in a solvent to produce an extrudable solution. The solution is then extruded through a die to form an elongated component and at least part of said solvent is removed from the elongated component. The polyethylene powder used in the process is produced by polymerizing ethylene in the presence of a catalyst composition comprising a Group 4 metal complex of a phenolate ether ligand.

Description

High molecular weight polyethylene fiber and film, their production and purposes

Technical field

The present invention relates to high molecular weight polyethylene fiber and film, their production and purposes.

Background technology

Term " High molecular weight polyethylene " usually is used for defining to have through ASTM 4020 measuring at least 3x10 ⁵The polyethylene of g/mol molecular weight, and expectation as used herein comprises that very High molecular weight polyethylene or VHMWPE (usually are characterized by to have through ASTM 4020 and measure at least 1x10 ⁶G/mol and less than 3x10 ⁶The polyethylene of g/mol molecular weight) and ultra-high molecular weight polyethylene or UHMWPE (usually be characterized by to have through ASTM 4020 and measure at least 3x10 ⁶The polyethylene of g/mol molecular weight).

High molecular weight polyethylene is valuable engineering plastics, and it has the unique combination of ABRASION RESISTANCE, surface lubrication, chemical resistance and impact strength.As a result of, they are for the preparation of high strength fibre, described fiber be used for rope and bounce-back road (anti-ballistic) moulded products and for the preparation of the goods of other elongation such as the film that is used for lithium battery.Yet, because these materials reduce with the molecular weight increase in the flowability of molten state, be not possible always the routine techniques processing is extruded such as fusing.

Produce fiber and comprise that with other elongation component High molecular weight polyethylene a kind of standby selection method of VHMWPE and UHMWPE is to pass through gel spinning, wherein polymer is dissolved in solvent, the gained gel extruded form fiber or film, then from part or all of product desolventizing.Dry products can be below the polyethylene fusing point the temperature of rising stretch to increase its tensile strength (also being toughness) and stretch modulus (also being elastic modelling quantity).The example of said method is disclosed in for example U.S. Patent number 5,741,451 and U.S. Patent Application Publication No. 2004/0161605.

Usually, the intensity molecular weight of polyethylene fiber increases, but for the polyethylene of conventionally form such as produce by Ziegler-Natta catalyst those, the solubility of this material in conventional ratio of solvent such as decahydronaphthalene and mineral oil increases with molecular weight and reduces.In addition, increase poly molecular weight and can follow coalescent during gelatinization process.Thereby polymer beads tends to lyosoption, causes particle to expand and entanglement, forms thus agglomerate.These gel particle networks that more or less move tend to adhere to for example extruder surface, thereby can cause difficult treatment to increase the energy of extrusion such as obstruction and needs.Gel particle also is final film or the potential source of the defective in the fiber.

According to the present invention, to find at present then may produce High molecular weight polyethylene by polymerising ethylene in the presence of the catalyst of the 4 family's metal complexs that comprise phenates ether, it has the solubility that basically is independent of molecular weight in decahydronaphthalene and other hydrocarbon solvent.Therefore, resulting polymers wishes to be used for Gel Treatment especially, so reason is to produce higher molecular weight and stronger fiber and film, and does not significantly increase the processing time.

Brief summary of the invention

On the one hand, the invention reside in for generation of the method for the polyethylene component that elongates such as fiber or film, the method comprises:

(a) will have at least 3x10 through ASTM 4020 mensuration ⁵The polyethylene powders of the molecular weight of g/mol is dissolved in solvent producing extrudable solution,

(b) extrude the component that described solution elongates with formation through mould, and

(c) remove at least a portion of described solvent from the component of described elongation,

Wherein said polyethylene powders produces by polymerising ethylene in the presence of the carbon monoxide-olefin polymeric of the 4 family's metal complexs that comprise phenates ether part.

Easily, polyethylene powders has through ASTM 4020 and measures at least 3x10 ⁵G/mol is such as 3x10 at least ⁶G/mol is such as about 3x10 ⁶G/mol is to about 10x10 ⁶The molecular weight of g/mol.

In one embodiment, the temperature of the rising of the component of described elongation below the polyethylene fusing point stretches.

Easily, 4 family's metal complexs are arranged on the bead-type substrate.Usually, bead-type substrate has less than 58 microns, and such as less than 50 microns, for example less than 30 microns, general about 4 to about 20 microns average particle size particle size d50.In one embodiment, bead-type substrate comprises inorganic oxide such as silica.

Easily, 4 family's metal complexs are complexs of two (phenates) ether part, such as the part of following following formula:

At least 2 is covalency wherein from oxygen (O) to the key of M, and other key is coordination; AR is the aromatic group that can be same or different from other AR group, and wherein each AR is independently selected from the optional aryl that is substituted and the optional heteroaryl that is substituted; B disregards hydrogen atom to have the bridged group of 3 to 50 atoms and be selected from the optional bivalent hydrocarbon radical that is substituted and the optional divalence that is substituted contains heteroatomic alkyl; M is the metal that is selected from Hf and Zr; Each L is the part that forms covalency, coordination or ionic bond with M independently; And n' is 1,2,3 or 4.

In one embodiment, two (phenates) ether part is followed following formula:

R wherein ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸And R ¹⁹Be selected from independently of one another hydrogen, halogen, and the optional alkyl that is substituted contain heteroatomic alkyl, alkoxyl, aryloxy group, silicyl, monoborane base, phosphino-, amino, alkylthio group, arylthio, nitro, and combination; Randomly two or more R groups can be combined as ring structure (for example, monocycle or multiring structure) together, and wherein said ring structure has 3 to 12 atoms (disregarding hydrogen atom) in the ring; And B disregards hydrogen atom to have the bridged group of 3 to 50 atoms and be selected from the optional bivalent hydrocarbon radical that is substituted and the optional divalence that is substituted contains heteroatomic alkyl.

Description of drawings

Fig. 1 is that the polyethylene product of embodiment 3 to 6 and the dissolution time of a series of commercial UHMWPE materials in mineral oil are to the figure of viscosity number (VN).

The detailed description of embodiment

Described herein is for having at least 3x10 from measuring through ASTM 4020 ⁵The polyethylene powders of the molecular weight of g/mol prepares the method for high strength fibre or film.The method involves polyethylene powders is dissolved in the solvent, with the gained gel spinning or extrude and form fiber or film and desolventizing.Described method adopts the polyethylene powders that polymerising ethylene produces in the presence of the carbon monoxide-olefin polymeric of the 4 family's metal complexs that comprise phenates ether part.Above-mentioned polymer is favourable, and reason is different from the High molecular weight polyethylene of routine, and its solvation time in most solvents generally all is independent of molecular weight, thereby reduces the processing time especially for higher molecular weight material.

Definition

As used herein, phrase " is expressed from the next " and is not intended to limit but uses " to comprise " identical mode with common use.Term " is independently selected from " and is used for pointing out in this article relevant group--for example, and R ¹, R ², R ³, R ⁴And R ⁵--can be identical or different (for example, R ¹, R ², R ³, R ⁴And R ⁵Can all be the alkyl that replaces, or R ¹And R ²Can be the alkyl that replaces and R ³Can be aryl etc.).The use of odd number comprises the use of plural number and vice versa (for example hexane solvent comprises various hexanes).The R group of name generally has the structure that the correspondence of admitting this area has the R group of this name.Term " compound " and " complex " be Alternate in this manual generally, but those skilled in the art will recognize that some compound is complex and vice versa.Be intended to presented for purpose of illustration some group of this paper define and represent.These definition expectations replenish and explanation but do not get rid of definition well known by persons skilled in the art.

Event or environment that " optional " or " randomly " means to describe subsequently can occur or can not occur, and described description comprises the situation that situation that described event or environment occur and described event or environment do not occur.For example, phrase " optional be substituted alkyl " means that hydrocarbyl portion can or can not be substituted and this description comprises the alkyl that is unsubstituted and the alkyl that wherein has replacement.

Term " alkyl " is as used herein to refer to branching or nonbranched saturated hydrocarbons group, and it usually but not necessarily contain 1 to about 50 carbon atoms, such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, octyl group, decyl etc., and cycloalkyl is such as cyclopentyl, cyclohexyl etc.Usually, although not necessarily, this paper alkyl can contain 1 to about 20 carbon atoms." replace alkyl " refers to the alkyl (for example benzyl or chloromethyl) that replaces with one or more substituting groups, and term " contains heteroatomic alkyl " and " assorted alkyl " refers to alkyl, wherein at least one carbon atom with the hetero atom replacement (for example ,-CH ₂OCH ₃The example of assorted alkyl).

Term " thiazolinyl " is as used herein to refer to branching or nonbranched hydrocarbyl group, and it usually but not necessarily contain 2 to about 50 carbon atoms and at least one two key, such as vinyl, positive propenyl, isopropenyl, n-butene base, isobutenyl, octenyl, decene base etc.Usually, although not necessarily, this paper thiazolinyl contains 2 to about 20 carbon atoms." thiazolinyl that replaces " refers to the thiazolinyl with one or more substituting groups replacements, and term " contains heteroatomic thiazolinyl " and " assorted thiazolinyl " refers to thiazolinyl, and wherein at least one carbon atom is replaced with hetero atom.

Term " alkynyl " is as used herein to refer to branching or nonbranched hydrocarbyl group, and it usually but not necessarily contain 2 to about 50 carbon atoms and at least one triple bond, such as acetenyl, positive propinyl, isopropyl alkynyl, positive butynyl, the isobutyl alkynyl, octyne base, decynyl etc.Usually, although not necessarily, this paper alkynyl can have 2 to about 20 carbon atoms." alkynyl that replaces " refers to the alkynyl with one or more substituting groups replacements, and term " contains heteroatomic alkynyl " and " assorted alkynyl " refers to alkynyl, and wherein at least one carbon atom is replaced with hetero atom.

Term " aromatics " uses with its common implication, comprises the basically unsaturated bond of delocalization on several keys around the ring.Term " aryl " group that refers to contain aromatic ring as used herein.This paper aryl comprises such group, and it contains single aromatic ring or many aromatic rings, and described polyaryl ring is to condense together, covalently bound or be connected to common group such as methylene or ethylidene part.More specific aryl contains 1 aromatic ring or 2 or 3 aromatic rings that condense or connect, for example phenyl, naphthyl, xenyl, anthryl or phenanthryl.In special embodiment, aryl substituent comprises that 1 to about 200 is not the atom of hydrogen, and usually 1 to about 50 is not the atom of hydrogen, and especially 1 to about 20 be not the atom of hydrogen.In some embodiment of this paper, many loop sections are substituting groups, and described in said embodiment many loop sections can connect in suitable atom place.For example, " naphthyl " can be 1-naphthyl or 2-naphthyl; " anthryl " can be the 1-anthryl, 2-anthryl or 9-anthryl; And " phenanthryl " can be the 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl.

Term " alkoxyl " alkyl that means to connect by single terminal ether combination as used herein; Also namely, " alkoxyl " group can be expressed as-the O-alkyl, and wherein alkyl such as preamble define.Term " aryloxy group " uses in a similar manner, and can be expressed as-the O-aryl, aryl such as hereinafter definition.Term " hydroxyl " refers to-OH.

Similarly, term " alkylthio group " alkyl that means to connect by single terminal thioether combination as used herein; Also namely, " alkylthio group " group can be expressed as-the S-alkyl, and wherein alkyl such as preamble define.Term " arylthio " uses in a similar manner, and can be expressed as-the S-aryl, wherein aryl such as hereinafter definition.Term " sulfydryl " refers to-SH.

Term " allene base " uses with conventional sense in this article, and it refers to have structure-CH=C=CH ₂Molecule fragment." allene base " group can be unsubstituted or replace with one or more non-hydrogen substituting groups.

Term " aryl " is as used herein, unless otherwise specified, refers to contain the aromatic substituent of single aromatic ring or many aromatic rings, and described many aromatic rings are that condense, covalently bound or are connected to common group such as methylene or ethylidene part.More specific aryl contains 1 aromatic ring or 2 or 3 aromatic rings that condense or connect, such as phenyl, naphthyl, xenyl, anthryl, phenanthryl etc.In special embodiment, aryl substituent has 1 to about 200 carbon atoms, and usually 1 to about 50 carbon atoms, and 1 to about 20 carbon atoms especially." aryl that replaces " refers to the aryl moiety with one or more substituting groups replacements, (for example tolyl, mesitylene base and perfluorophenyl), and term " contains heteroatomic aryl " and " heteroaryl " refers to aryl, wherein (term " heteroaryl " comprises for example various rings at least one carbon atom with the hetero atom replacement, such as the benzo-fused analog of thiophene, pyridine, pyrazine, isoxazole, pyrazoles, pyrroles, furans, thiazole, oxazole, imidazoles, isothiazole, oxadiazole, triazole etc. or these rings, such as indoles, carbazole, benzofuran, benzothiophene etc.).This paper in some embodiments, many loop sections are that substituting group and many in said embodiment loop sections can connect in suitable atom place.For example, " naphthyl " can be 1-naphthyl or 2-naphthyl; " anthryl " can be the 1-anthryl, 2-anthryl or 9-anthryl; And " phenanthryl " can be the 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl.

Term " halo " and " halogen " use with conventional sense, and it refers to chlorine, bromine, fluorine or iodine substituting group.

Term " heterocycle " and " heterocycle " refer to the ring-type residue, it comprises that ring condenses system, and described ring condenses system and comprises such as defined heteroaryl hereinafter, wherein the one or more carbon atoms in the ring with hetero atom replace-also be, not the atom of carbon, such as nitrogen, oxygen, sulphur, phosphorus, boron or silicon.Heterocycle and heterocyclic group comprise saturated and undersaturated part, comprise such as defined heteroaryl hereinafter.The particular instance of heterocycle comprises pyrrolidines, pyrrolin, and furans, oxolane, thiophene, imidazoles ， oxazole, thiazole, indoles etc. comprise their any isomers.Extra heterocycle is described in for example Alan R.Katritzky, Handbook of Heterocyclic Chemistry, PergammonPress, 1985, and Comprehensive Heterocyclic Chemistry, the people such as A.R.Katritzky write, Elsevier, 2d.ed. is in 1996.Term " becket compound " refers to heterocycle, wherein one or more the ring in hetero atom in one or more are metals.

Term " heteroaryl " refers to aromatic yl residue, comprises one or more hetero atoms in the aromatic ring.Specific heteroaryl comprises the group that contains heteroaromatic rings, described heteroaromatic rings is such as thiophene, pyridine, pyrazine, isoxazole, pyrazoles, pyrroles, furans, thiazole, oxazole, imidazoles, isothiazole, oxadiazole, triazole, and the benzo-fused analog of these rings is such as indoles, carbazole, benzofuran, benzothiophene etc.

That more generally, modifier " mix " or " contains is heteroatomic " and " assorted alkyl " or " " refer to molecule or molecule fragment, wherein one or more carbon atoms are replaced with hetero atom to contain heteroatomic alkyl.Such as term " assorted alkyl " refers to contain heteroatomic alkyl substituent therefore." contain heteroatomic " to introduce in a series of situations that may contain heteroatomic group at term, expect that this term application is in each member of described group.Also namely, phrase " contains heteroatomic alkyl, thiazolinyl and alkynyl " and is interpreted as " contains heteroatomic alkyl, contains heteroatomic thiazolinyl and contain heteroatomic alkynyl."

" alkyl " refers to hydrocarbyl residue, and it contains 1 to about 50 carbon atoms, and particularly 1 to about 24 carbon atoms, and the most particularly 1 to about 16 carbon atoms, comprise branching or nonbranched, saturated or unsaturated kind, such as alkyl, thiazolinyl, aryl etc.Term " lower alkyl " means 1 to 6 carbon atom, the particularly alkyl of 1 to 4 carbon atom.

Infer such as in the aforementioned definitions some, " replacement " in " alkyl that replaces ", " aryl that replaces ", " alkyl that replaces " etc. refers in described alkyl, alkyl, aryl or other parts, at least one is bonded to the hydrogen atom of carbon atom and replaces with one or more substituting groups, and described substituting group is such as hydroxyl, alkoxyl, alkylthio group, phosphino-, amino, halo, silicyl etc.In the situation before term " replacement " appears at a series of groups that may replace, expect that this term application is in each member of described group.Also namely, phrase " alkyl, thiazolinyl and the alkynyl that replace " is interpreted as " alkyl, the thiazolinyl of replacement and the alkynyl of replacement that replace ".Similarly, " optional alkyl, thiazolinyl and the alkynyl that is substituted " is interpreted as " the optional alkyl that is substituted, the optional thiazolinyl that is substituted and the optional alkynyl that is substituted ".

Term " saturated " refer between each atom of residue, not exist two keys and triple bond, such as ethyl, cyclohexyl, pyrrolidinyl etc.Term " undersaturated " refers to have one or more pairs of keys and triple bond between each atom of residue; such as vinyl, allyl, acetylide, oxazolinyl, cyclohexenyl group, acetyl group etc.; particularly comprise thiazolinyl and alkynyl; and the group of two key delocalizations wherein, such as hereinafter defined aryl and heteroaryl.

" divalence " in " bivalent hydrocarbon radical ", " divalent alkyl ", " divalent aryl " etc. refers to that described alkyl, alkyl, aryl or other parts are bonded to atom, molecule or part at two points, and wherein two Cheng Jiandian are covalent bonds.

Term as used herein " silicyl " refers to-SiZ ¹Z ²Z ³Residue, wherein Z ¹, Z ²And Z ³Be selected from independently of one another hydrogen and the optional alkyl that is substituted, thiazolinyl, alkynyl contains heteroatomic alkyl, contains heteroatomic thiazolinyl, contains heteroatomic alkynyl, aryl, heteroaryl, alkoxyl, aryloxy group, amino, silicyl and combination thereof.

Term as used herein " monoborane base " refers to-BZ ¹Z ²Group, wherein Z ¹And Z ²Respectively preamble defines freely.As used herein, term " phosphino-" refers to group-PZ ¹Z ², Z wherein ¹And Z ²Respectively preamble defines freely.As used herein, term " phosphine " refers to group-PZ ¹Z ²Z ³, Z wherein ¹, Z ²And Z ³Respectively preamble defines freely." amino " is used in reference to group-NZ to term in this article ¹Z ², Z wherein ¹And Z ²Respectively preamble defines freely.Term " amine " is used in reference to group-NZ in this article ¹Z ²Z ³, Z wherein ¹, Z ²And Z ³Respectively preamble defines freely.

Other abbreviation used herein comprises: " iPr " refers to isopropyl; " tBu " refers to the tert-butyl group; " Me " refers to methyl; " Et " refers to ethyl; " Ph " refers to phenyl; " Mes " refers to mesitylene base (2,4,6-trimethylphenyl); " TFA " refers to trifluoroacetate; " THF " refers to oxolane; " Np " refers to naphthyl; " Cbz " refers to carbazyl; " Ant " refers to anthryl; Refer to 1,2,3,4,5,6,7,8-octahydro anthryl with " H8-Ant "; " Bn " refers to benzyl; " Ac " refers to CH ₃CO; " EA " refers to ethyl acetate; " Ts " refers to the p-toluenesulfonyl of tosyl or synonym; " THP " refers to oxinane; " dppf " refers to 1,1 '-two (diphenylphosphino) ferrocene; " MOM " refers to methoxy.

" polyethylene " means 90% ethylene-derived units, or 95% ethylene-derived units, or the polymer of 100% ethylene-derived units formation.Thereby polyethylene can be homopolymers or the copolymer with other monomeric unit, comprises trimer.Such as polyethylene described herein can comprise at least a or multiple other alkene and/or comonomer.For example, in one embodiment, alkene can contain 3 to 16 carbon atoms; In another embodiment, contain 3 to 12 carbon atoms; In another embodiment, contain 4 to 10 carbon atoms; And in another embodiment, contain 4 to 8 carbon atoms.Exemplary comonomers includes, but not limited to propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 4-methylpent-1-alkene, 1-decene, 1-dodecylene, 1-hexadecylene etc.This paper can also use the polyene comonomer such as 1,3-hexadiene, Isosorbide-5-Nitrae-hexadiene, cyclopentadiene, dicyclopentadiene, 4-vinyl hexamethylene-1-alkene, 1,5-cyclo-octadiene, 5-ethenylidene-2-ENB and 5-vinyl-2-ENB.Other embodiment can comprise ethyl propylene acid esters or methacrylate.

" High molecular weight polyethylene " refers to that weight average molecular weight is at least about 3x10 ⁵The polyethylene composition of g/mol, and as used herein, and expectation comprises very High molecular weight polyethylene and ultra-high molecular weight polyethylene.For the intention of this specification, the mentioned molecular weight of this paper is determined (" Margolies molecular weight ") according to the Margolies formula.

" very High molecular weight polyethylene " refers to that weight average molecular weight is less than about 3x10 ⁶G/mol and greater than about 1x10 ⁶The polyethylene composition of g/mol.In some embodiments, very the molecular weight of High molecular weight polyethylene composition is about 2x10 ⁶G/mol is extremely less than about 3x10 ⁶G/mol.

" ultra-high molecular weight polyethylene " refers to that weight average molecular weight is at least about 3x10 ⁶The polyethylene composition of g/mol.In some embodiments, the molecular weight of ultra-high molecular weight polyvinyl composite is about 3x10 ⁶G/mol is to about 30x10 ⁶G/mol, or about 3x10 ⁶G/mol is to about 20x10 ⁶G/mol, or about 3x10 ⁶G/mol is to about 10x10 ⁶G/mol, or about 3x10 ⁶G/mol is to about 6x10 ⁶G/mol.

Term " bimodal " refer to polymer or polymer composition for example polyethylene have " bimodal molecular weight distribution." " is bimodal, and " composition can comprise the polyethylene component with at least a appraisable higher molecular weight and the polyethylene component with at least a appraisable lower molecular weight, for example two the different peaks (GPC chromatogram) on the SEC curve.Have the material that surpasses 2 kinds of different molecular weight distribution peaks and will be considered to used term " bimodal compositions ", but this material can also be called " multimodal " composition, such as three peak compositions or even four peak compositions etc.

Term in " bread molecular weight distribution " " wide " comprises such situation, wherein polyethylene composition comprises higher and admixture lower molecular weight component, but wherein on the SEC curve, there are not 2 obvious peaks (GPC chromatogram), but than wider unimodal of independent component peaks.

" ultra-high molecular weight polyethylene component " refers to have at least about 3x10 in bimodal (or multimodal) composition ⁶The polyethylene component of the weight average molecular weight of g/mol.In some embodiments, the ultra-high molecular weight polyethylene component has about 3x10 ⁶G/mol is to about 20x10 ⁶G/mol, or about 3x10 ⁶G/mol is to about 15x10 ⁶G/mol, or about 3x10 ⁶G/mol is to about 10x10 ⁶G/mol, or about 3x10 ⁶G/mol is to about 6x10 ⁶The weight average molecular weight of g/mol.Under composition comprises situation greater than 2 kinds of components, three peak compositions for example, this multimodal composition can have greater than a kind of super high molecular weight component.

" very High molecular weight polyethylene component " refers to that weight average molecular weight in bimodal (or multimodal) composition is less than about 3x10 ⁶G/mol is (for example less than about 2.5x10 ⁶G/mol or less than about 2.25x10 ⁶G/mol or less than about 2.0x10 ⁶G/mol) and greater than about 1x10 ⁶The polyethylene component of g/mol.

Part

The part that adopts in the catalyst system therefor in the inventive method can usually be defined as phenates ether part, more particularly is two (phenates) ether part.For example, the part that is applicable in the inventive method can characterize by following general formula:

Wherein each part has at least two hydrogen atoms, its can with the binding reaction of metallic atom or metal precursor or alkali in remove; AR is the aromatic group that can be same or different from other AR group, and wherein usually each AR is independently selected from the optional aryl that is substituted or the optional heteroaryl that is substituted; And B is the bridged group with 3 to 50 atoms (disregarding hydrogen atom).A kind of preferred embodiment in, B is about 3 bridges to about 20 carbon atoms (not comprising hydrogen atom).

Usually, " upper aromatic ring " is the ring that is bonded to of hydroxyl bond or the ring of its part.Similarly, " lower aromatic ring " is the ring that is bonded to of oxygen or the ring of its part.In some embodiments, AR-AR (also namely, the structure of 1 upper aromatic ring and corresponding lower aromatic ring formation thereof) is two aryl kind, more especially xenyls.

In some embodiments, bridged group B is selected from bivalent hydrocarbon radical and divalence and contains heteroatomic alkyl (for example comprise about 3 to about 20 carbon atoms), and it can be chosen wantonly and be substituted.In embodiment more particularly, B is selected from the optional divalent alkyl that is substituted, thiazolinyl, alkynyl, assorted alkyl, assorted thiazolinyl, assorted alkynyl, aryl, heteroaryl and silicyl.In these embodiments arbitrarily in, bridged group can enough one or more following radicals replace: the optional alkyl that is substituted or optional be substituted contain heteroatomic alkyl, such as the optional alkyl that is substituted, thiazolinyl, alkynyl, assorted alkyl, assorted thiazolinyl, assorted alkynyl, aryl or heteroaryl.It should be noted that above-mentioned replacement is not included in the key between formula I bridged group B and the oxygen atom.Alkyl or contain in the heteroatomic alkyl two or more and can connect the formation ring structure has 3 to 50 atoms (disregarding hydrogen atom) in the ring structure.Comprise in some embodiment of one or more ring structures at bridged group, may pick out more than one the expansion bridge atom chain from oxygen atom, and can conveniently described " bridge " be defined as in said case the shortest access path between the oxygen atom, and " substituting group " is defined as the group that is bonded to the bridge Atom.Exist in 2 kinds of situations for the access path of selecting same weak point, described bridge can be defined as along arbitrary path.

In other embodiments, B can be by general formula-(Q " R ⁴⁰ _{2-z "}) _Z'-representative, each Q wherein " be carbon or silicon independently, and each R wherein ⁴⁰Be independently selected from hydrogen and the optional alkyl that is substituted or choose the heteroatomic alkyl that contains that is substituted wantonly.Two or more R ⁴⁰Group can connect the formation ring structure, has 3 to 50 atoms (disregarding hydrogen atom) in this ring structure.In these embodiments, z ' is 1 to 10 integer, more special 1 to 5 integer, even the integer of more special 2-5, and z " is 0,1 or 2.For example, the R that " is 2 o'clock, does not have Q " at z and connect ⁴⁰Group, this allows those situations of one of them Q " multiple bond is bonded to second Q ".In more specific embodiment, R ⁴⁰Be selected from hydrogen, halogen, and the optional alkyl that is substituted, thiazolinyl, alkynyl, assorted alkyl, assorted thiazolinyl, assorted alkynyl, aryl, heteroaryl, alkoxyl, aryloxy group, silicyl, monoborane base, phosphino-, amino, alkylthio group, arylthio, and combination, wherein at least one R among the B ⁴⁰Group is not hydrogen.In embodiment mentioned above arbitrarily in, the B group can comprise one or more chiral centres.Therefore, for example, B can be by formula-CHR ⁵⁰-(CH ₂) _m-CHR ⁵¹-representative, wherein R ⁵⁰And R ⁵¹Be independently selected from the optional alkyl that is substituted, assorted alkyl, aryl or heteroaryl, R ⁵⁰And R ⁵¹Can be arranged as Arbitrary Relative configuration (such as cis/trans, Soviet Union's formula/erythro form etc.), and wherein this part can produce as racemic mixture or with enantiopure form.

In special embodiment, bridged group B comprises that expansion is from the chain of one or more bridge atoms of oxygen atom, and be adjacently located on one or more in the oxygen atom one or boths' the described bridge atom and be bonded to one or more substituting groups (disregard aforesaid be connected in the oxygen atom or both or along the key in abutting connection with bridge atom of chain), wherein said substituting group is independently selected from the optional alkyl that is substituted, assorted alkyl, aryl and heteroaryl.In embodiment more particularly, bridged group B replaces with a plurality of substituting groups, described substituting group is independently selected from the optional alkyl that is substituted, assorted alkyl, aryl and heteroaryl, thereby so that with oxygen atom in one or each bridge atom that both are adjacent be bonded at least one substituting group, still disregard and be connected to oxygen atom or in abutting connection with the key of bridge atom.In said embodiment, two or more in the substituting group can connect the formation ring structure, have 3 to 50 atoms (disregarding hydrogen atom) in the ring structure.

Therefore, in some embodiments, O-B-O fragment can characterize by one of following formula:

Wherein each Q is independently selected from carbon and silicon, each R ⁶⁰Be independently selected from hydrogen and the optional alkyl that is substituted and contain heteroatomic alkyl, condition is at least one R ⁶⁰Substituting group is not hydrogen, wherein said R ⁶⁰Substituting group randomly connects the formation ring structure, disregard hydrogen atom in the ring structure and have 3 to 50 atoms, and m ' is 0,1,2 or 3.Specific O-B in these embodiments-O fragment comprises for example O-(CH ₂) ₃-O, O-(CH ₂) ₄-O, O-CH (CH ₃)-CH (CH ₃)-O, O-CH ₂-CH (CH ₃)-CH ₂-O, O-CH ₂-C (CH ₃) ₂-CH ₂-O, O-CH ₂-CH (CHMe ₂)-CH ₂-O, O-CH ₂-CH (C ₆H ₅)-CH ₂-O, O-CH (CH ₃)-CH ₂-CH (CH ₃)-O, O-CH (C ₂H ₅)-CH ₂-CH (C ₂H ₅)-O, O-CH (CH ₃) CH ₂CH ₂CH (CH ₃)-O, O-CH (C ₆H ₅) CH ₂CH (C ₆H5 ₎-O,

Other specific bridging partly is described in the embodiment ligands and complexes of this paper.

In special embodiment, part can characterize by following formula:

R wherein ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸And R ¹⁹Be selected from independently of one another hydrogen, halogen, and the optional alkyl that is substituted contain heteroatomic alkyl, alkoxyl, aryloxy group, silicyl, monoborane base, phosphino-, amino, alkylthio group, arylthio, nitro, and combination; Randomly two or more R groups can be combined as ring structure (for example monocycle or multiring structure) together, and described ring structure has 3 to 12 atoms (disregarding hydrogen atom) in the ring; And B is such as the defined bridged group of preamble.

In more specific embodiment, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸And R ¹⁹Be independently selected from hydrogen, halogen, and the optional alkyl that is substituted, assorted alkyl, aryl, heteroaryl, alkoxyl, aryloxy group, silicyl, amino, alkylthio group and arylthio.In some embodiments, R ²And R ¹²In at least one is not hydrogen, and in other embodiments, R ²And R ¹²All not hydrogen.

In more specific embodiment, R ²And R ¹²Be selected from aryl and heteroaryl (for example phenyl of phenyl, replacement, anthryl carbazyl, mesitylene base, 3,5-(uncle-Bu) 2-phenyl etc.); R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸And R ¹⁹As hereinbefore defined; And B is:

Wherein Q, R ⁶⁰And m ' defines such as preamble.

In another specific embodiment, R ²And R ¹²Be independently selected from part replacement or that be unsubstituted of following general formula:

Wherein the break key of mark is the tie point to the molecule remainder; R ⁴And R ¹⁴Each is alkyl naturally; R ³, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹³, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸And R ¹⁹Be hydrogen, and B is selected from:

Exemplary construction only provides for the demonstration purpose, should not be considered as having restrictive sense.For example, one or more can the replacement with one or more substituting groups that are selected from such as Me, iPr, Ph, Bn, tBu etc. in the ring.

In more specific embodiment, part can characterize by following formula:

In formula III, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸And R ⁹Be selected from independently of one another hydrogen, halogen, and the optional alkyl that is substituted, thiazolinyl, alkynyl, assorted alkyl, assorted thiazolinyl, assorted alkynyl, aryl, heteroaryl, alkoxyl, aryloxy group, silicyl, monoborane base, phosphino-, amino, sulfydryl, alkylthio group and arylthio, nitro, and combination.Remaining substituent B as hereinbefore defined.

In more specific embodiment, R ²Be selected from aryl and heteroaryl; R ⁴It is alkyl; R ³, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹Hydrogen; And B is:

Wherein Q, R ⁶⁰And m ' defines such as preamble.

In another special embodiment, R ²Be selected from part replacement or that be unsubstituted of following general formula:

R ⁴It is alkyl; R ³, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹As hereinbefore defined; And B is selected from:

In one embodiment, part is selected from following structure:

The part preparation

In general, part disclosed herein prepares with known procedure, is described in for example March such as those, Advanced Organic Chemistry, Wiley, New York 1992 (4thEd.).More particularly, part of the present invention can enough various synthetic routes prepare, and it depends on the part modification of hope.Usually, each part is to assemble the preparation of formula approach: then the preparation structural unit directly or with bridged group connects together.The substituent variation of R group can be introduced in structural unit synthetic.The variation of the synthetic introducing bridge of available bridged group.The suitable part of preparation also has been described in detail in for example WO 03/091262, and WO 2005/0084106, and US 7,060,848, US7, and 091,292, US 7,126,031, and US 7,241,714, and US 7,241,715, and U.S. Patent Publication No. 2008/0269470; Incorporate its full content into this paper by quoting.

Metal precursor compound

In case form desirable part, can itself and metallic atom, ion, compound or other metal precursor compound is combined.For example, in some embodiments, metal precursor is the metal precursor of activation, this refer to metal precursor (being described below) with assistant ligand combination or with its reaction before with activator (being described below) combination or with its reaction.In some applications, with the combination of part metallizing thing or precursor phase, if form product then the product of described combination is uncertain.For example, can be side by side part and metal or metal precursor compound and reactant, activator, capturing agent etc. be added reaction vessel.In addition, before adding metal precursor or after adding metal precursor, can for example come modified ligand by hydrogenation reaction or some other method of modifying.

Usually, metal precursor compound can be passed through formula M (L) n and characterize, and wherein M is the metal that is selected from the periodic table of elements 4 families, more particularly is selected from Hf and Zr, particularly Zr.Each is independently selected from following part naturally L: hydrogen, halogen, the optional alkyl that is substituted, assorted alkyl, allyl, diene, thiazolinyl, assorted thiazolinyl, alkynyl, assorted alkynyl, aryl, heteroaryl, alkoxyl, aryloxy group, monoborane base, silicyl, amino, phosphino-, ether, thioether, phosphine, amine, carboxylate, alkylthio group, arylthio, 1,3-propanedione compound (1,3-dionate), oxalates, carbonate, nitrate, sulfate, and combination.Randomly, two or more L groups connect the formation ring structure.In the ligand L one or more can also ionic bonding to metal M, and for example, L can be the anion (for example, L can be selected to be combined with activator and be described below those anion) of non-coordination or loose" ligands or weak coordination; And randomly two or more L groups can link together in ring structure.(referring to such as people such as Marks, Chem.Rev.2000,100,1391-1434 wherein describes in detail these weak interactions has been discussed.) subscript n is 1,2,3,4,5 or 6.Metal precursor can be monomer, dimer or its more much higher aggressiveness.

Suitable hafnium and the particular instance of zirconium precursors include but not limited to: HfCl ₄, Hf (CH ₂Ph) ₄, Hf (CH ₂CMe ₃) ₄, Hf (CH ₂SiMe ₃) ₄, Hf (CH ₂Ph) ₃Cl, Hf (CH ₂CMe ₃) ₃Cl, Hf (CH ₂SiMe ₃) ₃Cl, Hf (CH ₂Ph) ₂Cl ₂, Hf (CH ₂CMe ₃) ₂Cl ₂, Hf (CH ₂SiMe ₃) ₂Cl ₂, Hf (NMe ₂) ₄, Hf (NEt ₂) ₄, Hf (N (SiMe ₃) ₂) ₂Cl ₂, Hf (N (SiMe ₃) CH ₂CH ₂CH ₂N (SiMe ₃)) Cl ₂, and Hf (N (Ph) CH ₂CH ₂CH ₂N (Ph)) Cl ₂, and ZrCl ₄, Zr (CH ₂Ph) ₄, Zr (CH ₂CMe ₃) ₄, Zr (CH ₂SiMe ₃) ₄, Zr (CH ₂Ph) ₃Cl, Zr (CH ₂CMe ₃) ₃Cl, Zr (CH ₂SiMe ₃) ₃Cl, Zr (CH ₂Ph) ₂Cl ₂, Zr (CH ₂CMe ₃) ₂Cl ₂, Zr (CH ₂SiMe ₃) ₂Cl ₂, Zr (NMe ₂) ₄, Zr (NEt ₂) ₄, Zr (NMe ₂) ₂Cl ₂, Zr (NEt ₂) ₂Cl ₂, Zr (N (SiMe ₃) ₂) ₂Cl ₂, Zr (N (SiMe ₃) CH ₂ZrCH ₂CH ₂N (SiMe ₃)) Cl ₂, and Zr (N (Ph) CH ₂CH ₂CH ₂N (Ph)) Cl ₂The Lewis base adducts of these examples also is suitable for use as metal precursor, and such as ether, amine, thioether, phosphine etc. is suitable for use as lewis base.Particular instance comprises HfCl ₄(THF) ₂, HfCl ₄(SMe ₂) ₂And Hf (CH ₂Ph) ₂Cl ₂(OEt ₂).The metal precursor of activation can be ion or zwitterionic compound, such as [M (CH ₂Ph) ₃ ⁺] [B (C ₆F ₅) ₄ ^-] or [M (CH ₂Ph) ₃ ⁺] [PhCH ₂B (C ₆F ₅) ₃ ^-], wherein M is Zr or Hf.Metal precursor or the described ionic compound of activation can prepare in the following manner: the people such as Pellecchia, Organometallics, 1994,13,298-302; The people such as Pellecchia, J.Am.Chem.Soc., 1993,115,1160-1162; The people such as Pellecchia, Organometallics, the people such as 1993,13,3773-3775 and Bochmann, Organometallics, 1993,12,633-640 incorporates it into this paper separately by quoting.

The ratio of part and metal precursor compound generally is about 0.1:1 to about 10:1, or about 0.5:1 about 5:1 extremely, or about 0.75:1 about 2.5:1 extremely, more particularly about 1:1.

Indication as mentioned, another aspect of the invention relates to the metal-ligand complex.Usually, before mixture is contacted with reactant (for example monomer) or side by side, part (or randomly as discussed above modified part) and the metal precursor that suits (with randomly other ratio of component such as activator) are mixed.With in part and the situation that metal precursor compound is mixed, can form the metal-ligand complex, its loaded catalyst that can be suitable for using according to the inventive method with formation with suitable activator load (perhaps altogether loaded catalyst).

The metal-ligand complex

Metal-ligand complex used herein can be described in many overlapping or standby modes of selecting.Thereby the metal-ligand complex can be described as having the complex of two anion chelands, and described two anion chelands can occupy 4 coordination sites of as many as of metallic atom.The metal ligand complex can also be described as having two anion ligands, and this part and metallic atom (metallic atom being counted one of member of heptatomic ring) form 2 seven yuan of becket compounds.In addition, in some embodiments, the metal-ligand complex can be described as having two anion chelands, described two anion chelands with oxygen as be connected to metallic atom in conjunction with atom.

In addition, in some embodiments, the metal-ligand complex can be described as having such part, and they can be with at least 2 kinds of approximate C ₂Symmetrical complex isomers mode coordination.Approximate C ₂Symmetry refers to part and metal-complexing, thereby each ligand moiety occupies metal center 4 quadrants on every side, with approximate C ₂Symmetrical mode is extended to ligand L; And can there be real symmetry in approximate referring to owing to affect symmetrical several factors, and described factor comprises for example impact of bridge.In these embodiments, the part conformation around the metal can be described as λ or δ.Can form at least 2 kinds of isomery complexs, it is each other mapping or non-mapping mutually.For the part that contains one or more chiral centres (for example, having the bridge of the replacement of chiral centre), can form diastereomeric metal ligand complex.The diastereomeric complex that is combined to form by special part-metal precursor can use as the mixture of diastereomer, perhaps can be separated and as the pure complex of diastereomer.

Can form dividually these heterogeneous structures: adopt the suitable metal precursor of the part (such as being described below chelating type diamides, biphenol or diene ligand) contain suitable replacement, the spatial chemistry that it can the strong effect complex reaction.Be known that, contain cheland 4 family's metal complexs can with the complex reaction of bridged bicyclic pentadienyl part in be used as metal precursor so that the spatial chemistry of control gained bridged metallocene complex, such as people such as Zhang, J.Am.Chem.Soc., 2000; 122,8093-8094, the people such as LoCoco, Organometallics, 2003,22,5498-5503, and the people such as Chen, J.Am.Chem.Soc., the description of 2004,126,42-43.The stereochemical mechanism that the 4 family's metal precursors that similarly contain the cheland of suitable replacement is used for can providing with the complex reaction of bridging two described herein (diaryl) part the metal-ligand complex that affects the roughly C2 of gained chirality symmetry.Use chirality 4 family's metal precursors of the cheland of the suitable replacement similarly contain the one or more chiral centres of tool that the mechanism of the absolute stereo chemistry of the metal-ligand complex that affects the roughly C2 of gained chirality symmetry can be provided.4 family's metal precursors of basically enantiomer-pure of cheland that use contains the suitable replacement of the one or more chiral centres of tool can provide the mechanism of the metal-ligand complex of the pure roughly C2 symmetry of preparation basically enantiomer of the present invention or diastereomer.

In some cases, can also be by carrying out the mixture that diastereomer/Chiral Separation comes enantiomer separation or diastereomer with chiral reagent.Referring to such as people such as Ringwald, J.Am.Chem.Soc., 1999,121, pp.1524-1527.

As polymerization catalyst the time, the complex of various diastereomers can have different polymerization usefulness, for example causes forming having wide/bimodal molecular weight and/or forming the polymeric articles that distributes.

In one embodiment, used metal-ligand complex can characterize by following formula in the catalyst of the present invention:

Wherein AR, M, L, B and n ' each freely preamble define; And dotted line is pointed out the possible combination to metallic atom, condition be in the dotted line at least two be covalent bond.

In this respect, should note Ln ' refer to metal M be bonded to quantity n ' such as the defined L group of preamble.

It shall yet further be noted that a kind of preferred embodiment in, B is about 3 bridges to about 50 carbon atoms (not comprising hydrogen atom), is more preferably about 3 bridges to about 20 carbon atoms.

More particularly, metal-ligand complex used herein can characterize by following formula:

R wherein ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸And R ¹⁹Each freely preamble structure (II) is defined, and M, L, n ', B such as preamble define and as for the further explanation of structure (V).Dotted line is pointed out the possible combination to metallic atom, condition be in the dotted line at least 2 be covalent bond.

The particular instance of suitable metal-ligand complex comprises:

The preparation of metal-ligand complex

The metal-ligand complex can form by technology well known by persons skilled in the art, such as providing under the condition of cooperation metal precursor and ligand combination.For example, complex of the present invention can be according to the preparation of the general approach shown in hereinafter:

As shown in scheme 13, causing removing under the condition of at least 2 leaving group ligand L, will be combined according to part and metal precursor M (L) n of formula II, described condition is shown in described scheme with hydrogen (H) and makes up.Can use other scheme of other known cooperation approach of employing, wherein with the combination of leaving group part and other parts (such as Li, Na etc.), described scheme comprises for example wherein with the reaction (for example wherein use the alkali metal salt of part and by salt elimination carry out complex reaction) of ligand L with the other parts reaction.

Catalyst carrier

Above-mentioned metal-ligand complex is carried on the bead-type substrate to obtain used loaded catalyst in the inventive method.Suitable carrier comprises silica, aluminium oxide, clay, zeolite, magnesium chloride, polystyrene, the polystyrene of replacement etc.Usually preferred inorganic oxide carrier, particularly silica supports.

Although the particle size of carrier is not key in the methods of the invention, the average particle size particle size d50 that usually wishes to guarantee carrier is less than 58 microns with usually less than 50 microns, for example less than 30 microns, such as about 4 to about 20 microns.Thereby general the discovery is controlled in the above-mentioned scope by the particle size with carrier, and then catalyst activity improves.

In addition, wish that in some cases carrier granular has log ₁₀(d ₉₀/ d ₁₀) span less than 0.6.

Before metal-loaded-ligand-complexes, generally with carrier with activator (such as in the following activator one or more), use especially organo-aluminum compound such as aikyiaiurnirsoxan beta methylaluminoxane (MAO) for example, process.Described processing can be included in preference temperature such as about 500 ℃ to about 900 ℃, and for example about 600 ℃, preferably at non-oxidizing atmosphere for example in the nitrogen environment, calcinated support.Then, product and for example toluene slurrying of suitable solvent through calcining can be added the activating substance source to it, be heated to about 50 ℃.After desolventizing and drying, obtain treated carrier, it is suitable for accepting the metal-ligand complex.

The metal-ligand complex is loaded on general such realization on the carrier: each component is dispersed in the liquid hydrocarbon, and with the combination of gained slurry, vortex stirring mixture about 1 was to about 3 hours under the anhydrous argon atmospher of protectiveness.

In one embodiment, to be deposited on the carrying capacity on the carrier be that about 1 μ mol/ gram loaded catalyst is to about 100 μ mol/ gram loaded catalyst to the metal-ligand complex.In another embodiment, carrying capacity is that about 2 μ mol/ gram loaded catalyst restrains loaded catalyst to about 100 μ mol/, and in another embodiment, carrying capacity is that about 4 μ mol/ gram loaded catalyst is to about 100 μ mol/ gram loaded catalyst.In another embodiment, the carrying capacity that the metal-ligand complex is deposited on the carrier is that about 1 μ mol/ gram loaded catalyst is to about 50 μ mol/ gram loaded catalyst.In another embodiment, carrying capacity is that about 2 μ mol/ gram loaded catalyst restrains loaded catalyst to about 50 μ mol/, and in another embodiment, carrying capacity is that about 4 μ mol/ gram loaded catalyst is to about 50 μ mol/ gram loaded catalyst.In other embodiments, the carrying capacity that the metal-ligand complex is deposited on the carrier is that about 1 μ mol/ gram loaded catalyst is to about 25 μ mol/ gram loaded catalyst, about 2 μ mol/ gram loaded catalyst is to about 25 μ mol/ gram loaded catalyst, and perhaps about 4 μ mol/ gram loaded catalyst is to about 25 μ mol/ gram loaded catalyst.In other embodiments, the carrying capacity that the metal ligand complex is deposited on the carrier is that about 1 μ mol/ gram loaded catalyst is to about 20 μ mol/ gram loaded catalyst, about 2 μ mol/ gram loaded catalyst is to about 20 μ mol/ gram loaded catalyst, and perhaps about 4 μ mol/ gram loaded catalyst is to about 20 μ mol/ gram loaded catalyst.In another embodiment, the carrying capacity that the metal-ligand complex is deposited on the carrier is that about 1 μ mol/ gram loaded catalyst is to about 15 μ mol/ gram loaded catalyst, about 2 μ mol/ gram loaded catalyst is to about 15 μ mol/ gram loaded catalyst, and perhaps about 4 μ mol/ gram loaded catalyst is to about 15 μ mol/ gram loaded catalyst.In extra embodiment, the carrying capacity that the metal ligand complex is deposited on the carrier is that about 1 μ mol/ gram loaded catalyst is to about 10 μ mol/ gram loaded catalyst, about 2 μ mol/ gram loaded catalyst is to about 10 μ mol/ gram loaded catalyst, perhaps in addition about 3 μ mol/ gram loaded catalyst to about 10 μ mol/ gram loaded catalyst.In other embodiments, the carrying capacity that the metal-ligand complex is deposited on the carrier is about 1 μ mol/ gram loaded catalyst, about 2 μ mol/ gram loaded catalyst, about 4 μ mol/ gram loaded catalyst, about 10 μ mol/ gram loaded catalyst, about 20 μ mol/ gram loaded catalyst, about 30 μ mol/ gram loaded catalyst, about 40 μ mol/ gram loaded catalyst, about 50 μ mol/ gram loaded catalyst or even about 100 μ mol/ gram loaded catalyst.

2 kinds of different metal-ligand complexs can be deposited on the organic or inorganic carrier to form altogether loaded catalyst of 2 components.Described 2 component catalysts are especially for the preparation of bimodal ultra-high molecular weight polyethylene.In one embodiment, to be deposited on the dead weight capacity on the carrier be that about 1 μ mol/ gram loaded catalyst is to about 100 μ mol/ gram loaded catalyst for 2 kinds of metal-ligand complexs.In another embodiment, the dead weight capacity that the metal-ligand complex is deposited on the carrier is that about 2 μ mol. gram loaded catalyst is to about 100 μ mol/ gram loaded catalyst; In another embodiment, be that about 4 μ mol/ gram loaded catalyst is to about 100 μ mol/ gram loaded catalyst.In one embodiment, to be deposited on the dead weight capacity on the carrier be that about 1 μ mol/ gram loaded catalyst is to about 50 μ mol/ gram loaded catalyst for 2 kinds of metal-ligand complexs.In another embodiment, the dead weight capacity that the metal-ligand complex is deposited on the carrier is that about 2 μ mol/ gram loaded catalyst is to about 50 μ mol/ gram loaded catalyst; In another embodiment, be that about 4 μ mol/ gram loaded catalyst is to about 50 μ mol/ gram loaded catalyst.In another embodiment, the carrying capacity that the metal ligand complex is deposited on the carrier is that about 1 μ mol/ gram loaded catalyst is to about 25 μ mol/ gram loaded catalyst, about 2 μ mol/ gram loaded catalyst is to about 25 μ mol/ gram loaded catalyst, and perhaps about 4 μ mol/ gram loaded catalyst is to about 25 μ mol/ gram loaded catalyst.In other embodiments, the carrying capacity that the metal ligand complex is deposited on the carrier is that about 1 μ mol/ gram loaded catalyst is to about 20 μ mol/ gram loaded catalyst, about 2 μ mol/ gram loaded catalyst is to about 20 μ mol/ gram loaded catalyst, and perhaps about 4 μ mol/ gram loaded catalyst is to about 20 μ mol/ gram loaded catalyst.In extra embodiment, the carrying capacity that the metal ligand complex is deposited on the carrier is that about 1 μ mol/ gram loaded catalyst is to about 10 μ mol/ gram loaded catalyst, about 2 μ mol/ gram loaded catalyst is to about 10 μ mol/ gram loaded catalyst, perhaps in addition about 4 μ mol/ gram loaded catalyst to about 10 μ mol/ gram loaded catalyst.In other embodiments, the carrying capacity that the metal-ligand complex is deposited on the carrier is about 1 μ mol/ gram loaded catalyst, about 2 μ mol/ gram loaded catalyst, about 4 μ mol/ gram loaded catalyst, about 10 μ mol/ gram loaded catalyst, about 20 μ mol/ gram loaded catalyst, about 30 μ mol/ gram loaded catalyst, about 40 μ mol/ gram loaded catalyst, about 50 μ mol/ gram loaded catalyst or even about 100 μ mol/ gram loaded catalyst.

Under 2 kinds of metal-ligand complexs were deposited on situation on the carrier, the mol ratio of the first complex and the second complex can be about 1:1, and perhaps alternatively, 2 set of dispense compounds of load can comprise the relatively alternative molar excess of a kind of complex.For example, the ratio of the first complex and the second complex can be about 1:2; About 1:3; About 1:5; About 1:10; About 1:20 or more.In one embodiment, being deposited on the first metal-ligand complex on the carrier and the ratio of the second metal-ligand complex is about 1:1 and 1:10; And this ratio is that about 1:1 is to about 1:5 in another embodiment.In addition, ratio can be regulated with the need, and can determine to obtain bimodal compositions by experiment, and it has the Target Splitting between high molecular weight component and low molecular weight polyethylene component.

The activator that is used for the metal-ligand complex

When combined with one or more suitable activators, above-mentioned metal-ligand complex is active polymerization catalyst.Broadly, activator can comprise aikyiaiurnirsoxan beta, lewis acid, Bronsted acid, compatible non-interfering activator and aforesaid combination.Instructed in the following list of references activator of these types is used together from different composition or metal complex, by quoting it is all incorporated into: US 5,599 herein, and 761, US 5,616,664, and US 5,453,410, US 5,153,157, US 5,064,802, EP-A-277,004 and the people such as Marks, Chem.Rev.2000,100,1391-1434.In some embodiments, preferred ion type or one-tenth ion-type activator.In other embodiments, preferred alumoxane activator.

Comprise CATION as the ionic compound that suits into of activator in one embodiment, it is the Bronsted acid that can supply with proton, and the anion of inertia, compatible, non-interfering, A-.Suitable anion includes but not limited to that consist of those of single coordinate complex, described complex comprises live metal or metalloid core.On mechanism, anion reply alkene formula, alkadienes and unsaturated compound or other neutral Lewis base are unstable fully such as substituting of ether or nitrile.Suitable metal includes but not limited to aluminium, gold and platinum.Suitable metalloid includes but not limited to boron, phosphorus and silicon.Certainly, the compound that contains the anion that consists of coordinate complex is known and is numerous, and described coordinate complex contains single metal or metalloid atom; Particularly, the described compound that contains single boron atom in the anionicsite is commercially available.

Especially, described activator can be represented by following general formula:

(L ^*—H) _d ⁺(A ^d-)

L wherein ^*It is neutral Lewis base; (L ^*-H)+be Bronsted acid; A ^D-The anion with electric charge d-that right and wrong are interfering, compatible, and d is 1 to 3 integer.More particularly, A ^D-Corresponding: (M' ³⁺Q _h) ^D-, wherein h is 4 to 6 integer; H-3=d; M' is the element that is selected from the periodic table of elements 13 families; And Q is independently selected from hydrogen, the dialkyl amide base, and halogen, alkoxyl, aryloxy group, alkyl, and the hydrocarbyl residue that replaces (comprising the alkyl that halogen replaces, such as fully halogenated hydrocarbyl residue), described Q has 20 carbon of as many as.In more specific embodiment, d is 1, also is that equilibrium ion has single negative electrical charge and corresponding to formula A-.

The activator that comprises boron or aluminium can be represented by following general formula:

(L ^*—H) ⁺(JQ ₄) ^-

Wherein: L ^*Define such as preamble; J is boron or aluminium; And Q is the C1-20 alkyl of fluoridizing.The most especially, Q is independently selected from the aryl of fluoridizing, and (also is C such as pentafluorophenyl group ₆F ₅Group) or 3,5-, two (CF ₃) ₂C ₆H ₃Group.Exemplary, but without limitation, the example that can be used as the boron compound of active cocatalyst in the preparation catalyst through improving of the present invention is trisubstituted ammonium salt such as tetraphenyl boric acid trimethyl ammonium, tetraphenyl boric acid triethyl ammonium, tetraphenyl boric acid tripropyl ammonium, tetraphenyl boric acid three (normal-butyl) ammonium, tetraphenyl boric acid three (tert-butyl group) ammonium, N, accelerine CATION tetraphenyl borate salts, N, N diethylaniline CATION tetraphenyl borate salts, N, accelerine CATION four-(3,5-two (trifluoromethyl) phenyl) borate, N, N-dimethyl-(2,4,6-trimethylaniline CATION) tetraphenyl borate salts, four (pentafluorophenyl group) boric acid trimethyl ammonium, four (pentafluorophenyl group) boric acid triethyl ammonium, four (pentafluorophenyl group) boric acid tripropyl ammonium, four (pentafluorophenyl group) boric acid three (normal-butyl) ammonium, four (pentafluorophenyl group) boric acid three (sec-butyl) ammonium, N, N dimethylaniline CATION four (pentafluorophenyl group) borate, N, N-diethylaniline CATION four (pentafluorophenyl group) borate, N, N-dimethyl-(2,4,6-trimethylaniline CATION) four (pentafluorophenyl group) borate, four-(2,3,4,6-phenyl tetrafluoride ylboronic acid trimethyl ammonium and DMA CATION four-(2,3,4,6-tetrafluoro phenyl) borate; Dialkyl ammonium salt is such as four (pentafluorophenyl group) boric acid two (isopropyl) ammonium, and four (pentafluorophenyl group) boric acid dicyclohexyl ammonium; With three replace De phosphonium salts such as four (pentafluorophenyl group) boric acid triphenyl phosphonium, four (pentafluorophenyl group) boric acid three (o-tolyl) Phosphonium, and four (pentafluorophenyl group) boric acid three (2,6-3,5-dimethylphenyl) Phosphonium; DMA CATION four (3,5-two (trifluoromethyl) phenyl) borate; HNMe (C ₁₈H ₃₇) ₂ ⁺B (C ₆F ₅) ₄ ^-HNPh (C ₁₈H ₃₇) ₂ ⁺B (C ₆F ₅) ₄ ^-((4-nBu-Ph) NH (n-hexyl) ₂) ⁺B (C ₆F ₅) ₄ ^-((4-nBu-Ph) NH (positive decyl) ₂) ⁺B (C ₆F ₅) ₄ ^-Specific (L ^*-H) ⁺CATION is N, and N-dialkyl aniline CATION is such as HNMe ₂Ph ⁺, the N of replacement, N-dialkyl aniline CATION is such as (4-nBu-C ₆H ₄) NH (just-C ₆H ₁₃) ₂ ⁺(4-nBu-C ₆H ₄) NH (just-C ₁₀H ₂₁) ₂ ⁺And HNMe (C ₁₈H ₃₇) ₂ ⁺The particular instance of anion is four (3,5-two (trifluoromethyl) phenyl) borate and four (pentafluorophenyl group) borate.In some embodiments, specific activator is PhNMe ₂H ⁺B (C ₆F ₅) ₄ ^-

Other suitable one-tenth ion-type activator comprises the cation oxidant of following formula representative and the salt of anion non-interfering, compatible:

(Ox ^e+) _d(A ^d-) _e

Wherein: Oxe+ is the cation oxidant with electric charge e+; E is 1 to 3 integer; And A ^D-Define with d such as preamble.The example of cation oxidant comprises: ferrocene cation, the ferrocene cation of alkyl-replacement, Ag+, or Pb+2.The particular implementation of Ad-is about containing predefined those anion of active cocatalyst of Bronsted acid, particularly four (pentafluorophenyl group) borate.

Another suitable one-tenth ion-type active cocatalyst inclusion compound, it is the carbonium ion of following formula representative or the salt of anion silicyl CATION and non-interfering, compatible:

Wherein:

C1-100 carbonium ion or silicyl CATION; And A ^-Define such as preamble.Preferred carbonium ion is the trityl CATION, also is triphenyl carbon cation.The silicyl CATION can through type Z ⁴Z ⁵Z ⁶The Si+ CATION characterizes, wherein Z ⁴, Z ⁵And Z ⁶Be selected from independently of one another hydrogen, halogen, and the optional alkyl that is substituted, thiazolinyl, alkynyl, assorted alkyl, assorted thiazolinyl, assorted alkynyl, aryl, heteroaryl, alkoxyl, aryloxy group, silicyl, monoborane base, phosphino-, amino, sulfydryl, alkylthio group, arylthio, and combination.In some embodiments, the activator of appointment is Ph ₃C ⁺B (C ₆F ₅) ₄ ^-

The active cocatalyst inclusion compound that other is suitable, it is formula (A ^*+a) _b(Z ^*J ^* _j) ^-c _dThe salt of representative, wherein A ^*It is the CATION of electric charge+a; Z ^*Be 1 to 50, the anionic group of special 1 to 30 atom (disregarding hydrogen atom) also contains two or more lewis base sites; J ^*Be independently of one another and Z ^*The lewis acid of at least one lewis base site coordination, and two or more described J randomly ^*Group can be linked together in the part with a plurality of lewis acid degrees of functionality; J is 2 to 12 number; And a, b, c and d are 1 to 3 integers, and condition is that axb equals cxd.Referring to WO 99/42467, incorporate it into this paper by quoting.In other embodiments, the anionicsite of these active cocatalysts can characterize ((C by following formula ₆F ₅) ₃M " "-LN-M " " (C ₆F ₅) ₃) ^-, wherein M " " is boron or aluminium and LN is spacer group, it is selected from cyanide, azide, cdicynanmide and imidazole anion especially.Cationic moiety is quaternary amine in particular.Referring to for example, LaPointe waits the people, J.Am.Chem.Soc.2000, and 122,9560-9561 incorporates it into this paper by quoting.

In addition, suitable activator comprises lewis acid, such as being selected from three (aryl) borine, three (aryl of replacement) borine, three (aryl) aluminium alkane, those of three (aryl of replacement) aluminium alkane comprise that activator is such as three (pentafluorophenyl group) borine.Other useful one-tenth ion-type lewis acid comprises those with two or more lewis acid sites, such as being described in WO 99/06413 or Piers, " New Bifunctional Perfluoroaryl Boranes:Synthesis and Reactivity ofthe ortho-Phenylene-Bridged Diboranes 1,2-(B (C Deng the people ₆F ₅) ₂) ₂C ₆X ₄(X=H, F) ", J.Am.Chem.Soc., those of 1999,121,3244-3245 are all incorporated it into this paper by quoting.Other useful lewis acid those skilled in the art know that.Usually, Lewis acid activation agent group belongs in the ion-type activator group (although can find the exception of this general rule), and this group tends to get rid of 13 hereinafter listed family's reagent.Can use into the combination of ion-type activator.

Can use other general activator or compound for polymerisation.The activator of these compounds in can some situation, but can also bring into play other function in paradigmatic system is such as the alkylation metal center or catch impurity.These compounds belong to " activator " definition, but do not think into the ion-type activator herein.These compounds comprise can be by 13 family's reagent: G of following formula sign ¹³R ⁵⁰ _3-pD _p, G wherein ¹³Be selected from B, Al, Ga, In and combination thereof, p is 0,1 or 2, R ⁵⁰Be selected from independently of one another hydrogen, halogen, and the optional alkyl that is substituted, thiazolinyl, alkynyl, assorted alkyl, assorted thiazolinyl, assorted alkynyl, aryl, heteroaryl, and combination; And D is selected from halogen independently of one another, hydrogen, alkoxyl, aryloxy group, amino, sulfydryl, alkylthio group, arylthio, phosphino-and combination thereof.In other embodiments, 13 family's activators are oligomeric or high poly-aluminium alkoxide compounds, such as methylaluminoxane and known trim thereof.Referring to for example, Barron, " Alkylalumoxanes, Synthesis, Structure and Reactivity ", the 33-67 page or leaf, " Metallocene-Based Polyolefins:Preparation, Properties andTechnology ", J.Schiers and W.Kaminsky write, Wiley Series in PolymerScience, John Wiley﹠amp; Sons Ltd., Chichester, England, 2000, and the list of references that wherein draws.In other embodiments, can use the divalent metal reagent of following general formula definition: M ' R ⁵⁰ _2-p' D _{P '}, wherein p ' is 0 or 1 and R50 and D such as preamble define in this embodiment.M ' is metal and is selected from Mg, Ca, Sr, Ba, Zn, Cd and combination thereof.In other embodiments, can use formula M " R ⁵⁰The alkali metal reagent of definition, and R in this embodiment ⁵⁰Define such as preamble.M " is alkali metal and is selected from Li, Na, K, Rb, Cs and combination thereof.Extraly, in catalyst composition, can use hydrogen and/or silane or it is added paradigmatic system.Silane can through type SiR ⁵⁰ _4-qD _qCharacterize, wherein R ⁵⁰As hereinbefore defined, q is 1,2,3 or 4 and D such as preamble define, and condition is that at least one D is hydrogen.

The combination of activator or activator can be carried on the organic or inorganic carrier.Suitable carrier comprises silica, aluminium oxide, clay, zeolite, magnesium chloride, polystyrene, the polystyrene of replacement.Activator can with the common load of metal-ligand complex.Suitable carrier more completely is described in the above-mentioned part that is entitled as " catalyst carrier ".

The special metal that adopts: the mol ratio of activator (composition or complex are as catalyst) is 1:10, and 000 to 100:1,1:5000 to 10:1 more especially, the most special 1:10 to 1:1.In one embodiment of the invention, use the mixture, particularly 13 family's reagent and the combination that becomes the ion-type activator of above-claimed cpd.13 family's reagent and the mol ratio that becomes the ion-type activator be 1:10 particularly, and 000 to 1000:1, more especially 1:5000 to 100:1, the most particularly 1:100 to 100:1.In another embodiment, become ion-type activator and 13 family's reagent combined.Another embodiment is the combination of 13 family's reagent of above-claimed cpd and 5-30 equivalent, and described compound has the optional N that is substituted of about 1 equivalent, N-dialkyl aniline CATION four (pentafluorophenyl group) borate.In some embodiments, can use the oligomeric or high poly-alumoxane activator of about 30 to 2000 equivalents, such as modified aikyiaiurnirsoxan beta (for example alkylaluminoxane).

Slurry phase vinyl polymerization

With the combined situation of above-mentioned activator under, load type metal described herein-ligand-complexes catalyst is applicable in the slurry phase polymerisation of ethene especially well, and described polymerization produces very high and ultra-high molecular weight polyethylene or comprise at least a VHMWPE and the bimodal polymers composition of UHMWPE component.

In order to cause polymerization, the at first slurrying in suitable solvent with loaded catalyst and activator, described suitable solvent generally is to have about 4 to about 14 carbon atoms, such as about 8 liquid hydrocarbons to about 12 carbon atoms.In addition, the compound that effectively increases the hydrocarbon solvent electrical conductivity can with about 5 to less than the 40ppm solvent volume, add slurries such as about 20 amounts to about 30ppm solvent volume.Usually, this antistatic additive comprises at least a in polysulfone copolymer, polymerization polyamine and the oily soluble sulfonic acid.Suitable antistatic additive is

2,000 2500,3000,5000, or

2500,3000,5000,6000 or 6633, perhaps 163.Further, slurry can contain capturing agent, and such as alkyl magnesium compound, its amount is generally about 0.05mmol to about 16mmol, for example about 0.5mmol extremely about 16mmol/ rise hydrocarbon solvent.

Under polymerizing condition, the gained catalyst pulp is contacted with ethene, described polymerizing condition generally comprise about 20 ℃ to about 90 ℃ for example about 65 ℃ to about 85 ℃ temperature, and about 4 bar are to the pressure of about 40 bar, lasting about 15 minutes about 210 minutes time extremely.Generally with about 0% and the amount of the hydrogen of about 10% ethylene feed volume add hydrogen and control the poly molecular weight that is produced.

Polyethylene product

The product of above-mentioned slurry polymerization is polyethylene powders, and it has at least 3x10 that measures through ASTM 4020 ⁵G/mol is such as about 3x10 ⁵G/mol is to about 30x10 ⁶G/mol, or about 1x10 ⁶G/mol is to about 20x10 ⁶G/mol, or about 3x10 ⁶G/mol is to about 20x10 ⁶G/mol, or about 3x10 ⁶G/mol is to about 10x10 ⁶G/mol, or about 3x10 ⁶G/mol is to about 6x10 ⁶The molecular weight of g/mol.Powder can have monomodal molecular weight distribution or bimodal molecular weight distribution, has about 3x10 in a rear situation ⁶G/mol is to about 30x10 ⁶First's powder of the molecular weight of g/mol and have about 3x10 ⁵G/mol is to about 10x10 ⁶The second portion powder of the molecular weight of g/mol.Usually, the amount of the second lower molecular weight fraction is 0 to 40%.

In addition, polyethylene powders of the present invention usually has about 10 to about 1500 μ m, and general about 50 to about 1000 μ m, usually about 60 D to about 700 μ m ₅₀Average particle size particle size.In this respect, the polyethylene powders particle size mentioned of this paper is measured and is undertaken by the laser diffraction method according to ISO 13320.

The bulk density of polyethylene powders of the present invention generally is about 0.13 to about 0.5g/ml, generally is about 0.2 to about 0.5g/ml, and particularly about 0.25 to about 0.5g/ml.The polyethylene powders bulk density that this paper mentions is measured and is undertaken by DIN 53466.

In addition, polyethylene powders usually has about 60 to about 85% degree of crystallinity and about 2 to about 30 molecular weight distribution (Mw/Mn).

The generation of fiber and film

By Gel Treatment the gained polyethylene powders is formed ratio of component such as fiber or the film that elongates, wherein at first powder is dissolved in organic solvent to produce extrudable solution.Solvent generally is selected from aliphatic series and clicyclic hydrocarbon, such as octane, and nonane, decane and isomers thereof; Petroleum fractions; Mineral oil; Kerosene; Aromatic hydrocarbons is such as toluene, and dimethylbenzene, and naphthalene comprise that its hydrogenated derivatives is such as decahydronaphthalene and naphthane; Halogenated hydrocarbons is such as monochloro-benzene; With cycloalkane and cycloolefin, such as amphene, terpane, cinene, methyl cyclopentadiene, tristane, and 1,2,4,5-tetramethyl-Isosorbide-5-Nitrae-cyclohexadiene.The combination of the above-mentioned solvent of enumerating also can be used for the Gel Treatment of UHMWPE, and the combination of solvent also is called solvent simply.Extrudable solution usually contains 0.1 polymer to about 50 % by weight of having an appointment.

Then, at least a portion of through the mould of desired shape solution being extruded to form fiber or membrane component and removed described solvent from extrudate.Solvent removal process can be undertaken by known method, for example evaporates when for example decahydronaphthalene prepares UHMWPE solution or use extraction liquids, the perhaps combination of two kinds of methods when for example using paraffin at the spin solvent with relative volatility.If wish, temperature that can the rising below the polyethylene fusing point with gained fiber or film stretches to increase its strength and modulus.Environment temperature to about 155 ℃ and can use as many as 100 or even higher draw ratio for the preference temperature of stretched operation.

The present invention now more particularly describes with following non-limiting example.

In each embodiment, the dissolving test of UHMWPE sample is carried out with the Haake rheometer of being furnished with spiral agitator.Solvent for use is to degrade at duration of test avoiding with the slab oil of antioxidant (Irganox B225 0.5 % by weight) stabilisation.In solvent, dissolving is measured shear stress τ so that the solution of concentration 0.25 % by weight to be provided during course of dissolution with each UHMWPE sample dispersion.In solvent, stir polymer at 110 ℃ and dissolved in 30 minutes, this so that polymer be dispersed in the solvent fully.Then, mixture is heated to 120 ℃, continues 50 minutes, after this in 10 minutes, be heated to 220 ℃ and keep 170 minutes so that material is dissolved fully at 220 ℃.Because experimental condition and special agitator shape can be ignored Wei β enberg effect.

Begin at course of dissolution, observe the precipitous increase of shear stress, reason is that the gel particle that forms adheres to agitator a period of time and causes thus shear stress to increase.After a period of time, then shear stress is reduced to the final of substantial constant through maximum τ max

τ end, this points out that gel particle dissolves fully.In order to characterize the solvability of UHMWPE material, operation parameter τ max, τ end and ds=τ max/ τ end.

The viscosity number that embodiment quotes (VN) measure according to DIN EN ISO 1628 and directly and polymer molecular weight proportional.Thereby the VN of 500ml/g is corresponding to measuring about 5.6x10 through ASTM 4020 ⁵The molecular weight of gm/mol, the VN of 1000ml/g is corresponding to about 1.5x10 ⁶The VN of the molecular weight of gm/mol and 2000ml/g is corresponding to about 3.9x10 ⁶The molecular weight of gm/mol.

Embodiment 1: the preparation silica base carrier of PMAO Treatment with activating agent

To under nitrogen, place 8ml flicker bottle at 5 hours Davison XPO 2485 silica (500mg) of 600 ℃ of calcinings in advance.With silica slurrying in toluene (3.5mL), with the silica in PMAO-IP (Azko-Nobel) (the 1.5M toluene solution of 2.333mL) the adding vortex stirring/toluene slurry.At room temperature, with reactant mixture slurrying 30 minutes, then be heated to 50 ℃.Then, continuously vortex stirring and 50 ℃ of heating is removed toluene by nitrogen stream.After 2.5 hours, obtain anhydrous substances.At different 8mL bottles, above-mentioned preparation is repeated 3 times.Under vacuum 50 ℃ with material further dry extra 1 hour, obtain the silicon dioxide carried activator of PMAO-IP/ of 2.94g.The Al carrying capacity that the gained loaded catalyst has is the every gram of 4.98mmol Al PMAO-IP/ silica.

Embodiment 2: prepare silicon dioxide carried type catalyst

The catalyst that this embodiment adopts is the ZrCl with following formula ₂Two (phenates) ether complex:

It is synthetic that part is pressed the description of WO 2005/108406, and 80-100 ℃ in toluene with Zr (CH ₂Ph) ₂Cl ₂(EtO) cooperate 1-3 hour.Concentrated reaction mixture is cooled to-30 ℃ and spends the night.Before cooling, pentane is added concentrated toluene reaction mixture.Obtaining complex, is crystalline material.

In the 8ml bottle under vortex stirring, with gained complex (3.0ml, 4.0mM toluene solution, 12.0 μ mol) (300mg) slurry in heptane (3.0ml) of PMAO-IP/ silica (4.98mmolAl/g) that adds embodiment 1 preparation.With the slurry shake well, at room temperature vortex stirring is 2 hours, then at room temperature penetrates the logical little N2 stream of barrier film with pin and carries out drying.This spends about 1.5 hours.Drying should yellow (slightly being with orange) material under vacuum.The Al carrying capacity that the gained loaded catalyst has is that the every gram of 4.98mmol Al PMAO-IP/ silica and transition metal carrying capacity are the final catalyst of the every gram of 40umol.

Embodiment 3: vinyl polymerization

Carry out vinyl polymerization in 3 liters reactor, described reactor at first with the argon flushing, is then used hydrocarbon solvent (C ₈To C ₁₂The mixture of aliphatic hydrocarbon) mixture of (1.5 liters) and alkyl aluminum (TEA 200mmol/l) conditioning.After 15 to 30 minutes conditioning time, evacuation of liquid.What then, reactor is full of 2 liters hydrocarbon solvent and appropriate amount reaches the 30ppm concentration level

2000, under agitation (750rpm) is heated to 80 ℃.Flow down at nitrogen, with the triisobutyl aluminum solutions (TIBA of 100 % by weight of 2mL; 8mmol) add reactor, at the ethylene pressure pressurized reactor of 7 bar.

In glove box, 50mg loaded catalyst (the corresponding 2 μ mol metals) weighing of embodiment 2 is entered in the dropping funel, is suspended in the 30mL hydrocarbon solvent.Then, the inclusions with dropping funel under argon gas stream is transferred to metal cylinder, with cylinder sealing with pressurize under 9 bar argons.Then, catalyst suspension is injected in the reactor, monitoring parameter is such as temperature, ethene flow, ethylene pressure simultaneously.After injection, cylinder is washed with the 40mL hydrocarbon solvent.After 210 minute reaction time, close ethylene feed, reactor is cooled to room temperature, ventilation with nitrogen flushing 1 hour, is collected in polymer paste in the bucket.Then filter polymer, use washed with isopropyl alcohol, 80 ℃ of dried overnight.Obtain the free flowing powder of 123g yield, be equivalent to the catalyst activity of 2460g/g.This material has the VN of 970ml/g.

Embodiment 4: vinyl polymerization

Use the polymerizing condition identical with embodiment 3, but adding 256ml hydrogen.After 210 minute reaction time, close ethylene feed, reactor is cooled to room temperature, ventilation with nitrogen flushing 1 hour, is collected in polymer paste in the bucket.Then filter polymer, use washed with isopropyl alcohol, 80 ℃ of dried overnight.Obtain the free flowing powder of 122g yield, be equivalent to the catalyst activity of 2444g/g.This material has the VN of 1430ml/g.

Embodiment 5: vinyl polymerization

Use the polymerizing condition identical with embodiment 3, but only add 50ml hydrogen.After 210 minute reaction time, close ethylene feed, reactor is cooled to room temperature, ventilation with nitrogen flushing 1 hour, is collected into polymer paste in the bucket.Then filter polymer, use washed with isopropyl alcohol, 80 ℃ of dried overnight.Obtain the free flowing powder of 209g yield, be equivalent to the catalyst activity of 4180g/g.This material has the VN of 2610ml/g.

Embodiment 6: vinyl polymerization

Use the polymerizing condition identical with embodiment 3, but add only 30ml hydrogen.After 210 minute reaction time, close ethylene feed, reactor is cooled to room temperature, ventilation with nitrogen flushing 1 hour, is collected into polymer paste in the bucket.Then filter polymer, use washed with isopropyl alcohol, 80 ℃ of dried overnight.Obtain the free flowing powder of 234g yield, be equivalent to the catalyst activity of 4680g/g.This material has the VN of 2970ml/g.

Embodiment 7: solubility test

With the structure adaptability characteristic that obtains among the above-mentioned experimental measurement embodiment 3 to 6, and compare with the dissolution characteristics of commercial material GUR 4012 (VN=1100ml/g), GUR 4120 (VN=2100ml/g) and GUR 4030 (VN=3000ml/g).The results are shown in table 1 and Fig. 1, although the dissolution time of the commercial material of its demonstration depends on its molecular weight, in the situation of embodiment 3 to 6 products, its dissolution time is independent of molecular weight basically.

Table 1

Embodiment	VN[ml/g]	d50[μm]	t _e/ [dividing]
				3	970	384	174.7
4	1430	380	164
				5	2610	446	169.7
6	2970	506	175.5
				GUR?4012	1100	135	132
GUR?4120	2100	120	184
				GUR?4030	3000	120	217

Embodiment 8: vinyl polymerization

In this embodiment as the amplification form of embodiment 3 to 6 used polymerization processes, be ground to have 12.5 μ m average particle size particle size d50 silica as catalyst carrier.5,600ml hydrogen is added reactor.After 145 minute reaction time, obtain yield 3,750g flows freely polyethylene powders, is equivalent to the catalyst activity of 7,500g/g.

Polyethylene powders has the d50 (laser light scattering) of 264 μ m and the viscosity number according to DINEN ISO 1628 of 1,150ml/g.

Embodiment 9: the gel of embodiment 8 materials is extruded

Will be from the material of embodiment 8 and the mineral oil blend of 40 % by weight.Extrude the gained blend at the double helix extruder with 10 thermals treatment zone and length diameter ratio 60.Spiral characteristic comprises different mixing, shearing and Transfer Parameters.From 170 to 230 ℃ of variations of temperature profile in 10 thermals treatment zone are selected lower temperature at spray nozzle front end.Helix speed changes from 50-1000rpm.

Material is extruded film into thickness 0.5 to 1mm and width 100 to 125mm.Carry out extension test according to ISO 527, adopt according to DIN EN ISO 11542-2 to be used for measuring the test sample that elongates intensity.The result is summarized in the table 2, and it shows that the mechanical property of test sample is good and can compares with other material for generation of film.

Table 2

Embodiment 10: vinyl polymerization

In this embodiment as the amplification form of embodiment 3 – 6 used polymerization processes, be ground to have 12.5 μ m average particle size particle size d50 silica as catalyst carrier.Operate following carrying out: the ethylene partial pressure of 4.95 bar, the ethylene feed of 0.82kg/h provides the hydrogen of 1.31L/h simultaneously.The mobile polyethylene powders that gains freedom is equivalent to the catalyst activity of 6900g/g.

Polyethylene powders has the d50 (laser light scattering) of 282 μ m and the viscosity number according to DINEN ISO 1628 of 2,190ml/g.

Embodiment 11: vinyl polymerization

In this embodiment as the amplification form of embodiment 3 – 6 used polymerization processes, will be ground to the silica of the average particle size particle size d50 with 12.5 μ m as catalyst carrier.Operate following carrying out: the ethylene partial pressure of 3.99 bar, the ethylene feed of 0.85kg/h provides 0.97L/h hydrogen simultaneously.The mobile polyethylene powders that gains freedom is equivalent to the catalyst activity of 8950g/g.

Polyethylene powders has the d50 (laser light scattering) of 230 μ m and the viscosity number according to DINEN ISO 1628 of 2,590ml/g.

Embodiment 12: vinyl polymerization

Use the polymerizing condition identical with embodiment 3, but add only 30ml hydrogen.After 210 minute reaction time, close ethylene feed, reactor is cooled to room temperature, ventilation with nitrogen flushing 1 hour, is collected into polymer paste in the bucket.Then filter polymer, use washed with isopropyl alcohol, 80 ℃ of dried overnight.Obtain the free flowing powder of 551g yield, be equivalent to the catalyst activity of 11000g/g.This material has the VN of 3550ml/g.

Embodiment 13: the gel-spinning of material

The polyvinyl sample of embodiment 10 to 12 is dissolved in decahydronaphthalene, uses the flow program gel spinning.

At 150 ℃, in Brabender Prep-Center counter-rotating double spiral agitator, in 80rpm 300mL decahydronaphthalene and UHMWPE powder sample were mixed 28 minutes.Then, the UHMWPE gel with homogenize is transferred to (150 ℃) the piston extruder of preheating and allowed balance 20 minutes.With about 1m/min gelatinous fibre is extruded in 5 ℃ of n-hexanes baths of placing apart from mould outlet 1cm.Hydrogel filament was kept in n-hexane about 1 hour, and then at room temperature dry 24 hours to remove remaining decahydronaphthalene and hexane.

Then, make hydrogel filament stand two stage hot-drawns by the glycerine of heating.In two stages, will be held constant at 1.4m by the total path length of heating bath.The phase I stretching is carried out like this: at 120 ℃, and the charging rate of 4.49m/min and the gathering speed of 135m/min (draw ratio=30).Second stage stretches and carries out like this: at 135 ℃, and the gathering speed that the charging rate of 0.219m/min and desired draw ratio determine.The maximal draw ratio of each sample was defined as before spinning threadling disconnects can collect at least maximum rate of 5m continuous fibers.

Extension test carries out one filament: the maximum of testing along at least 5 disconnections of long filament is lifted weight be averaged.The speed of lifting is controlled at about 0.05m/min.Amass acquisition diameter measurement value by the sample of weighing known length and with density 1 Calculation Section.

The result is summarized in the table 3, and its characteristic that also comprises the fiber that commercial Spectra S2000 fiber and commercial UHMWPE material GUR-4022 gel spinning and hot-drawn produce is as reference.

Table 3

Each sample shows that also gel very little diameter after extruding increases (mould expansion).

Claims

1. for generation of the method for the polyethylene component that elongates, the method comprises:

(a) will have at least 3x10 through ASTM 4020 mensuration ⁵The polyethylene powders of the molecular weight of g/mol is dissolved in the solvent producing extrudable solution,

2. the process of claim 1 wherein that described polyethylene powders has through ASTM 4020 measures at least 1x10 ⁶G/mol, preferably 3x10 at least ⁶G/mol, and more preferably 3x10 ⁶G/mol to 10x10 ⁶The molecular weight of g/mol.

3. claim 1 or 2 method, the component of wherein said elongation is fiber or film.

4. each method in the aforementioned claim, the temperature of the rising of the component of wherein said elongation below the polyethylene fusing point stretches.

5. each method of aforementioned claim, wherein said 4 family's metal complexs are arranged on the bead-type substrate.

6. the method for claim 5, wherein bead-type substrate has less than 58 microns, preferably less than 50 microns, is more preferably less than 30 microns, more preferably 4 to 20 microns average particle size particle size d50.

7. claim 5 or 6 method, wherein said bead-type substrate comprises inorganic oxide, preferred silica.

8. each method in the claim 5 to 7, the particle of wherein said carrier are basically spherical.

9. each method in the claim 5 to 8 is wherein processed the particle of described carrier with organo-aluminum compound, subsequently described 4 family's metal complexs are deposited on the described carrier.

10. each method in the aforementioned claim, wherein said 4 family's metal complexs are complexs of two (phenates) ether part.

11. each method in the aforementioned claim, wherein said 4 family's metal complexs have following general formula:

12. each method in the aforementioned claim, wherein said phenates ether part has following general formula:

13. each method in the aforementioned claim, wherein said phenates ether part is selected from:

14. each method in the aforementioned claim, wherein said 4 family's metals are zirconiums.

15. the fiber that each method produces in the aforementioned claim or film.